CN107464938A - A kind of molybdenum carbide/carbon composite with core shell structure and preparation method thereof and the application in lithium-air battery - Google Patents
A kind of molybdenum carbide/carbon composite with core shell structure and preparation method thereof and the application in lithium-air battery Download PDFInfo
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- CN107464938A CN107464938A CN201710639978.6A CN201710639978A CN107464938A CN 107464938 A CN107464938 A CN 107464938A CN 201710639978 A CN201710639978 A CN 201710639978A CN 107464938 A CN107464938 A CN 107464938A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Application the invention discloses a kind of molybdenum carbide/carbon composite with core shell structure and preparation method thereof and in lithium-air battery.The Combined Mining is used, and there is core shell structure, kernel and shell to be formed by the molybdenum carbide doping carbon material of porous surface, and its preparation method is to mix molybdate solution with resin solution, obtains suspension, and the suspension passes through solvent structure spherical precursor；The spherical precursor is placed in protective atmosphere; it is heat-treated at high temperature; produce conduct electricity very well, molybdenum carbide/carbon composite that specific surface area is big and catalytic activity is high; being used as lithium-air battery catalyst material has relatively low overpotential; height ratio capacity and excellent cycle performance; and its preparation method is simple, cost is cheap, has wide industrial applications prospect.
Description
Technical field
It is more particularly to a kind of that there is core the present invention relates to a kind of new lithium-air battery catalyst material and preparation method thereof
Molybdenum carbide/the carbon composite and preparation method of shell structure and porous surface, as well as catalysis material is in lithium-air battery
In application, belong to lithium-air battery field.
Background technology
Lithium ion battery produces as a kind of electrochemical energy storing device for occupying social leading position in portable electronic
Fast development is achieved in product (notebook computer, intelligent mobile equipment, tablet personal computer etc.), equally in electric automobile field also table
Reveal good development prospect.Domestic automobile industry possesses huge market, and basic demand of the people to electric automobile is once
Charging can travel 500km, and this requires the energy density of the lithium rechargeable battery applied to electric automobile to must be over 500Wh
kg-1.However, by the theoretical lithium storage content of positive and negative pole material itself (such as graphite is 372mA h/g, and cobalt acid lithium is 274mA h/g,
LiFePO4 is 176mA h/g) limitation, commercial Li-ion battery --- conventional lithium ion secondary cell (discharge and recharge at present
During, the abjection or insertion of lithium ion occur respectively for positive and negative pole material) energy density be difficult on existing basis
Larger breakthrough is obtained on (200~250Wh/kg).Therefore, for new type lithium ion secondary cell system exploitation gesture must
OK.In recent years, the research to new type lithium ion secondary cell system has been increasingly becoming the study hotspot of field of lithium ion battery.
In various new type lithium ion secondary cells (lithium-air battery, lithium-sulfur cell, lithium selenium cell etc.), lithium-air battery is high by its
Energy density (corresponding lithium metal is 11400Wh kg-1, corresponding Li2O2For 3458Wh kg-1, actual energy density estimation is reachable
800Wh kg-1) arouse great concern, and turn into a kind of most potential new type lithium ion secondary cell.
Important in lithium-air battery is its catalysis material, in existing various non-oxidized substance catalyst materials,
Metal carbides are one kind than having wide application prospects.Metal carbides are in nearest a period of time just by it has been proposed that may be used as
Lithium air battery positive electrode elctro-catalyst.(J.Mater.Chem.A, 2014,2 (27) such as Jiaxin Li:10634-10638.) logical
The method that ferrous oxalate is added into the polyacrylonitrile matrix for electrostatic spinning is crossed, the work combined using electrostatic spinning and carbonization
Skill, it is prepared for being loaded with Fe/Fe3C carbon fiber, due to Fe3C presence, composite is as lithium air battery positive electrode material
When, the discharge and recharge overpotential of battery is significantly reduced, and improve the cycle performance of battery.But the preparation method process is answered
It is miscellaneous, it is difficult to realize industrial production.
Above-mentioned carbide is applied to show good performance during lithium-air battery etc., but its preparation method is deposited mostly
It is harsh in synthesis condition, the shortcomings that pattern and material homogeneity whard to control；Molybdenum carbide is as a kind of new transition metal carbon
Compound obtains extensive concern because of it in performance good in terms of catalysis, its research result as lithium-air battery catalyst material
It must explore.
The content of the invention
The defects of existing for existing lithium-air battery catalyst material, of the invention first purpose is to be to provide one
The carbonization for the advantages that kind has core shell structure, porous surface, and conductive energy is good, specific surface area is big and catalytic activity is high
Molybdenum/carbon composite.
Another object of the present invention is the above-mentioned material for being to provide that a kind of technique is simple, cost is cheap, environment-friendly
Preparation method.
Third object of the present invention is to be to provide a kind of molybdenum carbide/carbon composite as lithium-air battery catalyst
The application of material, there is relatively low overpotential, higher charging and discharging capacity and excellent using lithium-air battery of its preparation
Stable circulation performance.
In order to realize above-mentioned technical purpose, the invention provides a kind of molybdenum carbide/carbon composite with core shell structure,
There is the composite core shell structure, kernel and shell to be formed by the molybdenum carbide doping carbon material of porous surface.
Molybdenum carbide/carbon composite of the present invention has nucleocapsid, loose structure, composite is had higher ratio surface
Product, the wetting contact area of electrode material and electrolyte can be increased, so as to the more avtive spots of exposure, improve composite
Catalytic activity, and the lithium peroxide that larger specific surface area again generates catalysis has enough space attachments, avoids its excessive
Ground is covered in catalyst surface and has a strong impact on the performance of catalyst performance, is advantageous to improve the stable circulation of lithium-air battery
Property.
Preferable scheme, the size of the kernel is 1~10 μm.
Preferable scheme, the thickness of the shell is 50~200nm.
Preferable scheme, the molybdenum carbide doping carbon material surface include mesoporous and micropore.In molybdenum carbide doping carbon material
Molybdenum carbide particles Uniform Doped porous carbon surface and inside.
More preferably scheme, the specific surface area of the molybdenum carbide/carbon composite with core shell structure for 100~
300m2/g。
, will present invention also offers a kind of preparation method of described molybdenum carbide/carbon composite with core shell structure
Molybdate solution mixes with resin solution, obtains suspension, and the suspension passes through solvent structure spherical precursor；It is described
Spherical precursor is placed in protective atmosphere, is heat-treated, produced under 750 DEG C of temperatures above.
Preferable scheme, the mass ratio of the resin in molybdate and resin solution in the molybdate solution is 1:2~
1:6。
More preferably scheme, the molybdate include at least one of ammonium molybdate, sodium molybdate, potassium molybdate.More preferably molybdenum
Hydrochlorate is ammonium molybdate.
More preferably scheme, the resin include phenolic resin and/or Lauxite.Preferable resin is phenolic resin.
Preferable scheme, the temperature of the solvent thermal reaction is 150~200 DEG C, and the time is 12~24h.
Preferable scheme, the temperature of the heat treatment is 750~1000 DEG C, and the time is 6~12h.
The phenolic resin or Lauxite of the present invention can directly be bought, and existing conventional method can also be used to synthesize,
Such as add formaldehyde into react in resorcinol and can obtain phenol resin solution, the mol ratio of formaldehyde and resorcinol is 3:1
~1:1.
Preferable scheme, after the solvent thermal reaction products therefrom is washed repeatedly using water and absolute ethyl alcohol, it is placed in 50~
Under 80 DEG C of temperature conditionss, 8~12h is dried in vacuo, that is, obtains spherical precursor.
Preferable scheme, the protective atmosphere are nitrogen and/or argon gas atmosphere, preferably argon gas atmosphere.
The method that molybdenum carbide/carbon composite with core shell structure is prepared in technical scheme is to use solvent
Hot method combination high-temperature heat treatment.Solvent-thermal method key is to prepare suspension, and suspension is the key to form spheric granules presoma,
It is that templated deposition load molybdenum source obtains spherical precursor by resin, then it is unformed by high temperature cabonization, the generation of resin in-situ carburization
Carbon, molybdenum source is reduced into molybdenum carbide, and carbonisation keeps the original basic structure and microscopic appearance of presoma, generates porous
Molybdenum carbide/carbon composite with core shell structure.
In the preparation process of molybdenum carbide/carbon composite of the present invention, resin is taken full advantage of as carbon source and template
Effect, on the one hand, resin forms suspension as template, spherical precursor is obtained by solvent-thermal method, on the other hand, in high temperature
In carbonisation, resin generation carbon, then molybdenum source in-situ reducing is generated into molybdenum carbide, the spherical structure of resin formation had both been remained,
It is made full use of to participate in reacting as carbon source again, reduction molybdenum source generation molybdenum carbide.Unnecessary carbon and molybdenum carbide knot as reaction
Close closely, under the high temperature conditions, a part of amorphous carbon is converted into graphited carbon, so as to improve the conduction of composite
Property.Meanwhile in high-temperature burning process, due to being reacted in ball, internal stress is larger, core shell structure is gradually formed, and by
Gas is produced in the decomposition of ammonium molybdate and organic matter etc., loose structure is easily formed, it is more satisfactory to ensure that composite has
Specific surface area.The porous material structure of the nucleocapsid of formation can not only add the wetting contact face of electrode material and electrolyte
Product, makes it have enough catalytic reaction activity sites, and the lithium peroxide that bigger specific surface area again generates catalysis has enough
Space attachment, avoid it from being covered in catalyst surface too much and have a strong impact on the performance of catalyst performance, be advantageous to improve
The cyclical stability of lithium-air battery.
The preparation method of molybdenum carbide/carbon composite with core shell structure of the present invention includes step in detail below：
(1) a certain amount of 37% formalin is added in the beaker containing 3.85g resorcinols, stirring forms phenolic aldehyde
Resin solution；
(2) molybdate containing metal molybdenum is completely dissolved in deionized water, is then added slowly to above-mentioned phenolic aldehyde tree
In lipoprotein solution, stirring, suspension is formed；
(3) above-mentioned suspension is moved in ptfe autoclave liner and is allowed to carry out solvent thermal reaction, through centrifugation, washed
Wash, after drying, you can obtain spherical precursor；
(4) gained spherical precursor is placed in vacuum tube furnace under argon atmosphere, carries out high temperature cabonization, produce porous
Molybdenum carbide/carbon composite of core shell structure.
Present invention also offers the application of described molybdenum carbide/carbon composite with core shell structure, as lithium
O for cathode of air battery materials application.
The present invention prepares lithium-air battery and performance test methods using molybdenum carbide/carbon composite：Weigh above-mentioned material,
10wt.%Super P are added as conductive agent, 10wt.% Kynoar (PVDF) is used as binding agent, it is ground it is abundant after
Add a small amount of 1-METHYLPYRROLIDONE (NMP) and be mixed to form uniform black paste slurry, slurry is coated at through watery hydrochloric acid
As test electrode on the nickel screen collector managed, with metal lithium sheet, electrode assembling turns into 2032 button cells as a comparison, its
Electrolyte system is used as 1M LiTFSI/TEGDME, the barrier film used is GF/D fibreglass diaphragm, test loop performance institute
It is 1mA/cm with charging and discharging currents density2。
Compared with the prior art, the beneficial effect that technical scheme is brought：
1) molybdenum carbide/carbon composite of the invention has porous, core shell structure, composite is had higher ratio table
Area, the wetting contact area of electrode material and electrolyte can be increased, so as to the more avtive spots of exposure, improve composite wood
The catalytic activity of material, and the lithium peroxide that larger specific surface area again generates catalysis has enough space attachments, avoids its mistake
It is covered in catalyst surface more and has a strong impact on the performance of catalyst performance, is advantageous to improve the stable circulation of lithium-air battery
Property.
2) present invention prepares the method for molybdenum carbide/carbon composite operation is simple and reliable, it is reproducible, environment-friendly, into
This is cheap, has wide industrial applications prospect.
3) molybdenum carbide/carbon composite of the invention is particularly adapted to use as lithium-air battery catalysis material, prepares
Lithium-air battery there is relatively low overpotential, higher charging and discharging capacity and excellent stable circulation performance.
Brief description of the drawings
【Fig. 1】For the X-ray diffractogram (XRD) of molybdenum carbide/carbon composite made from embodiment 1；
【Fig. 2】For the scanning electron microscope (SEM) photograph (SEM) of molybdenum carbide/carbon composite made from embodiment 1；
【Fig. 3】For the graph of pore diameter distribution of molybdenum carbide/carbon composite made from embodiment 1；
【Fig. 4】For the constant current charge-discharge performance of the lithium-air battery of molybdenum carbide made from embodiment 1/carbon composite assembling
Figure；
【Fig. 5】For the cycle performance figure of the lithium-air battery of molybdenum carbide made from embodiment 1/carbon composite assembling.
【Fig. 6】For the scanning electron microscope (SEM) photograph (SEM) of carbon ball made from comparative example 1；
【Fig. 7】For the X-ray diffractogram (XRD) of molybdenum dioxide/carbon composite made from comparative example 2.
Embodiment
Following examples are intended to be described in further details present invention；And the protection domain of the claims in the present invention
It is not limited by the example.
Embodiment 1
3.85g resorcinols are weighed first, are added in beaker, then measure 5mL, and 37% formalin is added drop-wise to burning
In cup, stirring forms phenol resin solution.Weigh 1.236g ammonium molybdates be dissolved in 60mL water formed ammonium molybdate solution be added to
State in phenol resin solution, gained mixing suspension be transferred in polytetrafluoroethylene (PTFE) solvent thermal reaction kettle after stirring,
Solvent thermal reaction is carried out under the conditions of 160 DEG C, is washed gained sediment repeatedly through water and ethanol after reaction 18h, drying is
It can obtain spherical presoma.
Appropriate spherical precursor is weighed, is put it into inside corundum porcelain boat, and in dislocation vacuum tube furnace.It is passed through argon gas,
Tube furnace is warming up to 850 DEG C of heat treatment 6h, produces molybdenum carbide/carbon composite.
Button cell is assembled into using lithium-air battery molybdenum carbide/carbon composite manufactured in the present embodiment and lithium, its material
Expect structural characterization and chemical property as shown in the figure：
In Fig. 1 contrast standard diffracting spectrum illustrate in molybdenum carbide/carbon composite without other impurities, be single crystalline substance
Body.
It can be seen that molybdenum carbide/the carbon composite prepared has porous spherical nano-core-shell structure in Fig. 2, its
Middle molybdenum carbide/carbon composite particle size is 2~4 μm, and the specific surface area of molybdenum carbide/carbon composite is 296m2/g。
In Fig. 3 it can be seen that the pore size distribution of molybdenum carbide/carbon composite prepared mainly with micropore and it is mesoporous based on.
Show the electrode made using molybdenum carbide/carbon composite in Fig. 4, in 1mA/cm2Constant-current discharge density under, its
First circle specific capacity reaches 7980mA h/g, and its overpotential is only 1.07V.
Show the electrode made using molybdenum carbide/carbon composite in Fig. 5, in 1mA/cm2Constant-current discharge density under, follow
Capacity is decayed after ring 60 encloses, and shows good cyclical stability.
Embodiment 2
3.85g resorcinols are weighed first, are added in beaker, then measure 6mL, and 37% formalin is added drop-wise to burning
In cup, stirring forms phenol resin solution.Weigh 1.236g ammonium molybdates be dissolved in 60mL water formed ammonium molybdate solution be added to
State in phenol resin solution, gained mixing suspension be transferred in polytetrafluoroethylene (PTFE) solvent thermal reaction kettle after stirring,
Solvent thermal reaction is carried out under the conditions of 180 DEG C, is washed gained sediment repeatedly through water and ethanol after reaction 14h, drying is
It can obtain spherical presoma.
Appropriate spherical precursor is weighed, is put it into inside corundum porcelain boat, and in dislocation vacuum tube furnace.It is passed through argon gas,
Tube furnace is warming up to 800 DEG C of heat treatment 8h, produces molybdenum carbide/carbon composite.
Molybdenum carbide/carbon composite prepared by this method belongs to single crystal.The material part pattern is rendered as porous
Core shell structure, its nanoparticle size are 2~6 μm, and the specific surface area of molybdenum carbide/carbon composite is 207m2/g。
Button cell is assembled into using lithium-air battery catalyst material manufactured in the present embodiment and lithium piece, in 1mA/cm2
Constant-current discharge density under, circulation 48 circle after capacity decay.
Embodiment 3
3.85g resorcinols are weighed first, are added in beaker, then measure 4mL, and 37% formalin is added drop-wise to burning
In cup, stirring forms phenol resin solution.Weigh 1.854g ammonium molybdates be dissolved in 60mL water formed ammonium molybdate solution be added to
State in phenol resin solution, gained mixing suspension be transferred in polytetrafluoroethylene (PTFE) solvent thermal reaction kettle after stirring,
Solvent thermal reaction is carried out under the conditions of 180 DEG C, is washed gained sediment repeatedly through water and ethanol after reaction 20h, drying is
It can obtain spherical presoma.
Appropriate spherical precursor is weighed, is put it into inside corundum porcelain boat, and in dislocation vacuum tube furnace.It is passed through argon gas,
Tube furnace is warming up to 850 DEG C of heat treatment 8h, produces molybdenum carbide/carbon composite.
Molybdenum carbide/carbon composite prepared by this method belongs to single crystal.The material part pattern is rendered as porous
Core shell structure, its nanoparticle size are 3~5 μm, and the specific surface area of molybdenum carbide/carbon composite is 256m2/g。
Button cell is assembled into using lithium-air battery catalyst material manufactured in the present embodiment and lithium piece, in 1mA/cm2
Constant-current discharge density under, circulation 50 circle after capacity decay.
Embodiment 4
3.85g resorcinols are weighed first, are added in beaker, then measure 3mL, and 37% formalin is added drop-wise to burning
In cup, stirring forms phenol resin solution.Weigh 0.824g ammonium molybdates be dissolved in 60mL water formed ammonium molybdate solution be added to
State in phenol resin solution, gained mixing suspension be transferred in polytetrafluoroethylene (PTFE) solvent thermal reaction kettle after stirring,
Solvent thermal reaction is carried out under the conditions of 200 DEG C, is washed gained sediment repeatedly through water and ethanol after reaction 12h, drying is
It can obtain spherical presoma.
Appropriate spherical precursor is weighed, is put it into inside corundum porcelain boat, and in dislocation vacuum tube furnace.It is passed through argon gas,
Tube furnace is warming up to 900 DEG C of heat treatment 6h, produces molybdenum carbide/carbon composite.
Molybdenum carbide/carbon composite prepared by this method belongs to single crystal.The material part pattern is rendered as porous
Core shell structure, its nanoparticle size are 2~5 μm, and the specific surface area of molybdenum carbide/carbon composite is 273m2/g。
Button cell is assembled into using lithium-air battery catalyst material manufactured in the present embodiment and lithium piece, in 1mA/cm2
Constant-current discharge density under, circulation 54 circle after capacity decay.
Embodiment 5
3.85g resorcinols are weighed first, are added in beaker, then measure 5mL, and 37% formalin is added drop-wise to burning
In cup, stirring forms phenol resin solution.Weigh 1.648g ammonium molybdates be dissolved in 60mL water formed ammonium molybdate solution be added to
State in phenol resin solution, gained mixing suspension be transferred in polytetrafluoroethylene (PTFE) solvent thermal reaction kettle after stirring,
Solvent thermal reaction is carried out under the conditions of 200 DEG C, is washed gained sediment repeatedly through water and ethanol after reaction 18h, drying is
It can obtain spherical presoma.
Appropriate spherical precursor is weighed, is put it into inside corundum porcelain boat, and in dislocation vacuum tube furnace.It is passed through argon gas,
Tube furnace is warming up to 950 DEG C of heat treatment 12h, produces molybdenum carbide/carbon composite.
Molybdenum carbide/carbon composite prepared by this method belongs to single crystal.The material part pattern is rendered as porous
Core shell structure, its nanoparticle size are 5~10 μm, and the specific surface area of molybdenum carbide/carbon composite is 178m2/g。
Button cell is assembled into using lithium-air battery catalyst material manufactured in the present embodiment and lithium piece, in 1mA/cm2
Constant-current discharge density under, circulation 36 circle after capacity decay.
Comparative example 1
3.85g resorcinols are weighed first, are added in beaker, then measure 5mL, and 37% formalin is added drop-wise to burning
In cup, stirring forms phenol resin solution.Gained mixing suspension is transferred to polytetrafluoroethylene (PTFE) solvent heat after stirring
In reactor, solvent thermal reaction is carried out under the conditions of 160 DEG C, washes gained sediment repeatedly through water and ethanol after reaction 18h
Wash, dry and can obtain spherical presoma.
Appropriate spherical precursor is weighed, is put it into inside corundum porcelain boat, and in dislocation vacuum tube furnace.It is passed through argon gas,
Tube furnace is warming up to 850 DEG C of heat treatment 6h, produces carbon material.
Carbon material prepared by this method belongs to single carbon ball.The material part pattern is rendered as solid construction, its nanometer
Particle size is 2~4 μm, and the specific surface area of molybdenum carbide/carbon composite is 354m2/g。
Button cell is assembled into using lithium-air battery catalyst material manufactured in the present embodiment and lithium piece, in 1mA/cm2
Constant-current discharge density under, circulation 20 circle after capacity decay.
Comparative example 2
3.85g resorcinols are weighed first, are added in beaker, then measure 5mL, and 37% formalin is added drop-wise to burning
In cup, stirring forms phenol resin solution.Weigh 1.236g ammonium molybdates be dissolved in 60mL water formed ammonium molybdate solution be added to
State in phenol resin solution, gained mixing suspension be transferred in polytetrafluoroethylene (PTFE) solvent thermal reaction kettle after stirring,
Solvent thermal reaction is carried out under the conditions of 160 DEG C, is washed gained sediment repeatedly through water and ethanol after reaction 18h, drying is
It can obtain spherical presoma.
Appropriate spherical precursor is weighed, is put it into inside corundum porcelain boat, and in dislocation vacuum tube furnace.It is passed through argon gas,
Tube furnace is warming up to 700 DEG C of heat treatment 6h, produces molybdenum dioxide/carbon composite.
Composite prepared by this method belongs to single molybdenum dioxide/carbon crystal.The material part pattern is rendered as more
The core shell structure in hole, its nanoparticle size are 3~5 μm, and the specific surface area of molybdenum dioxide/carbon composite is 307m2/g。
Button cell is assembled into using lithium-air battery catalyst material manufactured in the present embodiment and lithium piece, in 1mA/cm2
Constant-current discharge density under, circulation 30 circle after capacity decay.
Claims (10)
- A kind of 1. molybdenum carbide/carbon composite with core shell structure, it is characterised in that：With core shell structure, kernel and shell Formed by the molybdenum carbide doping carbon material of porous surface.
- 2. according to claim 1 have core shell structure molybdenum carbide/carbon composite, it is characterised in that：The kernel Size is 1~10 μm, and the thickness of the shell is 50~200nm.
- 3. according to claim 1 have core shell structure molybdenum carbide/carbon composite, it is characterised in that：The molybdenum carbide Doping carbon material surface includes mesoporous and micropore.
- 4. molybdenum carbide/carbon composite with core shell structure according to any one of claims 1 to 3, it is characterised in that： The specific surface area of the molybdenum carbide/carbon composite with core shell structure is 100~300m2/g。
- 5. the preparation method of molybdenum carbide/carbon composite with core shell structure described in any one of Claims 1 to 4, it is special Sign is：Molybdate solution is mixed with resin solution, obtains suspension, the suspension by solvent structure it is spherical before Drive body；The spherical precursor is placed in protective atmosphere, is heat-treated, produced under 750 DEG C of temperatures above.
- 6. the preparation method of molybdenum carbide/carbon composite according to claim 5 with core shell structure, its feature exist In：The mass ratio of molybdate in the molybdate solution and the resin in the resin solution is 1:2~1:6.
- 7. the preparation method of molybdenum carbide/carbon composite according to claim 6 with core shell structure, its feature exist In：The molybdate includes at least one of ammonium molybdate, sodium molybdate, potassium molybdate；The resin includes phenolic resin and/or Lauxite.
- 8. the preparation method of molybdenum carbide/carbon composite with core shell structure according to any one of claim 5~7, It is characterized in that：The temperature of the solvent thermal reaction is 150~200 DEG C, and the time is 12~24h.
- 9. the preparation method of molybdenum carbide/carbon composite with core shell structure according to any one of claim 5~7, It is characterized in that：The temperature of the heat treatment is 750~1000 DEG C, and the time is 6~12h.
- 10. the application of molybdenum carbide/carbon composite with core shell structure described in any one of Claims 1 to 5, its feature exist In：As lithium air battery positive electrode materials application.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108808021A (en) * | 2018-06-08 | 2018-11-13 | 中国石油大学(华东) | Mo2C/C nanocomposites and preparation method thereof and lithium carbon dioxide anode and preparation method thereof comprising the material |
| CN108950874A (en) * | 2018-07-27 | 2018-12-07 | 中原工学院 | A kind of preparation method of the modified high hollow nanometer gradient activated carbon fiber film of ortho position thermosetting phenolic base of molybdic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108808021A (en) * | 2018-06-08 | 2018-11-13 | 中国石油大学(华东) | Mo2C/C nanocomposites and preparation method thereof and lithium carbon dioxide anode and preparation method thereof comprising the material |
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| CN108950874B (en) * | 2018-07-27 | 2020-03-10 | 中原工学院 | Preparation method of molybdic acid modified high-ortho thermosetting phenolic-based hollow nano gradient activated carbon fiber membrane |
| CN110854477A (en) * | 2019-11-22 | 2020-02-28 | 中国科学院物理研究所 | Mixed active metal ion/metal-oxygen battery system, construction method and application thereof |
| CN113072070A (en) * | 2021-03-26 | 2021-07-06 | 华东理工大学 | Preparation method of high-specific-surface-area carbon-coated transition metal carbide material |
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